JP2005279344A - Method for manufacturing laminated product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To generate no fisheye failure on a film surface of a coating film even if a coating liquid containing a compound having a large number of polymerizable unsaturated bonds is thin film-coated by a gravure coating system with high flat surface property of the coating film and to stably perform coating for a long period of time. <P>SOLUTION: In the method for manufacturing the laminated product, when one or more layers of films are formed on a continuously conveyed web 4 to make the laminated product, at least one layer thereof is a hard film layer formed by coating a coating liquid 2 containing the compound having the polymerizable unsaturated bond by a gravure coating device 10 and drying it by a drying device 8. When an amount of the polymerizable unsaturated bond is represented by acrylic equivalent, acrylic equivalent of a solid content in the coating liquid 2 is 3,200 (g/mol) or smaller. Under the coating condition wherein a film thickness of the film dried state of the coated layer is 200 nm, quality of the contact part with at least gravure roll 1 of a doctor blade 3 for pressing onto a gravure roll 1 surface of the gravure coating device 10 and scraping off the excessive coating liquid just before coating is resin or a composite material in which a resin, a fiber reinforcement material and a filling material are made composite. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  In the present invention, when forming a laminate by forming one or more films on a continuous support (hereinafter referred to as “web”), at least one of the compounds has a polymerizable unsaturated bond. Method of manufacturing a laminate, which is a hard film layer formed by applying a coating liquid containing a coating with a gravure coating apparatus and then drying with a drying apparatus, and an antireflection film manufactured by the manufacturing method, and using the antireflection film And an image display device in which the antireflection film or the polarizing plate is disposed on an image display surface.

  In recent years, in the field of various optical functional films such as an optical compensation film used as a retardation plate in a liquid crystal cell, an antireflection film, an antiglare film, etc., the film thickness is 200 nm or less, particularly in a dry film state. There is a demand for stable application on a web in an ultra-thin area. In addition, it is required to give a higher degree of added value to a film to be applied, and a film having a high hardness characteristic can be given as a representative value added.

  An example of a coating method with high suitability for thin film coating is a gravure coating method. In the gravure coating method, the coating liquid is supplied to the surface of the gravure roll on which the concavo-convex engraving has been applied, and after the surplus coating liquid on the surface of the gravure roll is scraped off by a doctor blade pressed against the surface of the gravure roll, This is a coating method in which the coating liquid remaining in the recesses is transferred onto the web. For example, Patent Document 1 discloses that an antireflection film is applied by a microgravure coating method, and an ultrathin film having a dry film thickness of 80 to 90 nm is applied. When performing thin film coating, doctor blades are mainly made of metal, but especially when applying ultra-thin films as described above, film thickness accuracy is important, so dimensional stability and work accuracy can be increased. A metal doctor blade is used.

By the way, as a technique for increasing the hardness of the coating film for increasing the added value described above, a method of increasing the cross-linking point density by applying a coating liquid containing a compound having many polymerizable unsaturated bonds to the web, A method for improving the film hardness of the coating film by adding a filler such as silica is known as general knowledge. Of these two methods, the addition of colloidal silica inevitably adversely affects the surface condition of the coating film due to aggregation, so a coating solution containing a compound having many polymerizable unsaturated bonds is applied. Thus, it is desirable to increase the hardness of the coating film.
JP 2003-322703 A

  However, when a coating solution containing a compound having many polymerizable unsaturated bonds is applied to the web using a gravure coating method, the surface of the coated film after coating becomes whitish, and when observed with an optical microscope, the diameter is about 3 μm. There is a case in which a defect occurs on the entire film surface. As a result, even if the film can be made highly hardened, there is a drawback that the quality of the coating film is significantly deteriorated due to the generated defect. Therefore, in the case where the laminate having such a defective layer is, for example, a functional film, there is a problem that optical characteristics required for the functional film are impaired.

  The present invention has been made in view of such circumstances, and even if a coating liquid containing a compound having a large number of polymerizable unsaturated bonds is applied by a gravure coating method, a flaw failure occurs on the film surface of the coating film. Furthermore, since the coating film has high flatness and can be stably applied for a long time, the quality of the laminate having at least one layer coated with the coating solution having the polymerizable unsaturated bond, for example, optical characteristics A method for producing a laminate capable of hardening without damaging the film, an antireflection film produced by the production method, a polarizing plate using the antireflection film, and the antireflection film or the polarizing plate An object is to provide an image display device disposed on an image display surface.

  According to claim 1 of the present invention, in order to achieve the above-mentioned object, when forming a laminated body by forming one or more films on a continuously-supported elongated support, at least one of them is not polymerizable. In the method for producing a laminate, which is a hard film layer formed by applying a coating liquid containing a compound having a saturated bond with a gravure coating apparatus, drying with a drying apparatus and then curing, the amount of the polymerizable unsaturated bond is determined. Under application conditions where the acrylic equivalent of solid content in the coating solution is 3200 (g / mol) or less when expressed in terms of acrylic equivalent, and the dry film thickness of the applied layer is 200 nm or less The material of at least the contact portion of the doctor blade that presses against the gravure roll surface of the gravure coating apparatus and scrapes off the excess coating solution in advance of coating is resin, or resin and fiber reinforcing material / filler. It is a composite material in which fillers are combined.

  The present inventor has intensively studied the cause of blister failure that occurs when a coating solution containing a compound having many polymerizable unsaturated bonds is applied to a web using a gravure coating method. It was found that the three factors of the amount of polymerizable unsaturated bonds per minute, the film thickness in the applied dry film state, and the material of the doctor blade significantly influence the occurrence of the blister failure. That is, when the amount of polymerizable unsaturated bonds is expressed in terms of acrylic equivalent, the acrylic equivalent of the solid content in the coating solution is 3200 (g / mol) or less, and the thickness of the applied layer in the dry state is Under coating conditions of 200 nm or less, a blister failure occurs when the material of at least the contact part of the doctor blade with the gravure roll is a metal, and the material is a resin or a composite of resin and a fiber reinforcing material / filler It was found that no faults occurred in the case of materials. This is because, in the case of an ultra-thin film of 200 nm or less in the dry film state, the defects appear on the film surface, so that the failure of the defects becomes obvious, and the acrylic equivalent of the solid content in the coating liquid is 3200 (g / mol). This is because when the amount of the polymerizable unsaturated bond is increased to the following level, a blistering failure starts to occur. Here, the acrylic equivalent is defined by the weight of the composition when 1 mol of polymerizable unsaturated bonds in a composition is collected, and is expressed in units of (g / mol). That is, it means that the smaller the acrylic equivalent, the larger the amount of polymerizable unsaturated bonds in the solid matter in the coating solution. The entire doctor blade may be a resin or a composite material in which a resin and a fiber reinforcing material / filler are combined.

  According to claim 1 of the present invention, since it is configured as described above, even if a coating solution containing a compound having many polymerizable unsaturated bonds is applied by a gravure coating method, the surface of the coating film is flawed. The film can be hardened without impairing the quality of the laminate having at least one layer coated with the coating solution having the polymerizable unsaturated bond, for example, the optical characteristics. Can do. In this case, it is also possible to use a metal doctor blade under application conditions that deviate from the above acrylic equivalent and film thickness. However, the present invention is particularly effective in producing a high-quality functional film in recent demands for laminates, for example, thinning and hardening of functional films.

A second aspect of the present invention is the first aspect of the present invention, wherein the material of at least the contact portion of the doctor blade has a wear test result of 30 (by the Taber abrasion test (wear wheel: CS-17, test load: 1000 g, rotation speed: 1000 revolutions)). mg / 10 ³ cycle) The material satisfies the following requirements.

Claim 2 defines the frictional wear resistance of the material of at least the contact part of the doctor blade with the gravure roll, and the result of the Taber abrasion test method (as defined in ASTM D 1044) is 30 (mg / 10 ³ cycle ) Frictional wear resistance is very high if the material satisfies the following conditions. As a result, the dimensional stability of the doctor blade can be ensured, so even if the doctor blade is pressed against the gravure roll surface by continuous long-time application, the state change due to wear of the contact portion with the gravure roll can be extremely reduced. . Therefore, even if it is an ultra-thin film application of 200 nm or less in a dry film state, stable application with good film thickness accuracy can be performed.

  A third aspect of the present invention is characterized in that, in the first or second aspect, the doctor blade has a water absorption rate of 1.0 (%) or less after the doctor blade is immersed in water for 24 hours.

  Claim 3 prescribes the water absorption rate of the doctor blade. When a resin doctor blade is used instead of the metal doctor blade, the dimensional stability of the doctor blade becomes a problem, so the water absorption rate is small. Good film thickness accuracy can be achieved by selecting the material. The water absorption test method is a value measured using the method specified in ASTM D570.

A fourth aspect of the present invention is characterized in that, in any one of the first to third aspects, the universal hardness of the layer coated with the coating liquid containing the compound having a polymerizable unsaturated bond is 100 (N / mm ² ) or more. And

  The fourth aspect defines a preferable film hardness of a layer coated with a coating solution containing a compound having a polymerizable unsaturated bond.

  A fifth aspect of the present invention is characterized in that in any one of the first to fourth aspects, the material of at least the contact portion of the doctor blade is a polyacetal resin.

  According to the fifth aspect of the present invention, the material of at least the contact portion of the doctor blade with the gravure roll is specified as polyacetal resin among various resins. This is because polyacetal resin has high frictional wear resistance, low water absorption, and relatively high moldability, so that it is possible to improve the flatness of the doctor blade, and it is possible to apply stably for a long time. This is because a sufficient film thickness accuracy can be achieved.

  A sixth aspect of the present invention is characterized in that, in any one of the first to fourth aspects, the material of at least the contact portion of the doctor blade is a polybutylene terephthalate resin.

  In the sixth aspect, the material of at least the contact portion of the doctor blade with the gravure roll is specified as polybutylene terephthalate resin among various resins. This is because polybutylene terephthalate resin has high frictional wear resistance, low water absorption, and relatively high moldability, so that the flatness of the doctor blade can be improved and stable application can be achieved for a long time. In addition, good film thickness accuracy can be achieved.

  A seventh aspect of the present invention is characterized in that, in any one of the first to fourth aspects, the material of at least the contact portion of the doctor blade is an ultrahigh molecular weight polyethylene resin.

  According to the seventh aspect of the present invention, the material of at least the contact portion of the doctor blade with the gravure roll is specified as an ultra high molecular weight polyethylene resin among various resins. This is because the ultra-high molecular weight polyethylene has an average molecular weight of 3 to 5 million by the viscosity method, which is extremely large compared to 20,000 to 300,000 of a general high-density polyethylene resin. This is because the frictional wear property is high and the water absorption rate is small, so that stable coating can be achieved for a long time and good film thickness accuracy can be achieved.

  An eighth aspect according to any one of the first to seventh aspects, wherein the compound having a polymerizable unsaturated bond contains at least one kind of polymerizable unsaturated bond group-containing polymerization component and fluorine-containing polymerization component. It is a combination.

  Claim 8 is particularly severe when the compound having a polymerizable unsaturated bond is a copolymer containing at least one of the polymerizable unsaturated bond group-containing polymerization component and the fluorine-containing polymerization component, This is because the effect of the present invention is particularly great.

  A ninth aspect of the present invention is an antireflection film produced by the method for producing a laminate according to any one of the first to eighth aspects in order to achieve the object.

  According to the ninth aspect of the present invention, an antireflection film with high display quality can be manufactured.

  A tenth aspect of the present invention is a polarizing plate in which a polarizing film is produced using the antireflection film according to the ninth aspect in order to achieve the above object.

  According to the tenth aspect of the present invention, a polarizing plate having a high display quality can be produced by producing a polarizing plate using the antireflection film produced in the ninth aspect.

  According to an eleventh aspect of the present invention, in order to achieve the above object, the antireflection film according to the ninth aspect or the polarizing plate according to the tenth aspect is disposed on an image display surface. It is.

  According to claim 11 of the present invention, an image display device having a high display quality can be obtained by manufacturing an image display device using the antireflection film manufactured in claim 9 or the polarizing plate manufactured in claim 10. Can be obtained.

  As described above, according to the method for manufacturing a laminate of the present invention, even if a coating solution containing a compound having a large number of polymerizable unsaturated bonds is applied by a gravure coating method, a failure occurs on the film surface of the coating film. Does not occur, and the flatness of the coating film is high and can be stably applied for a long time, so the quality of the laminate having at least one layer coated with the coating solution having the polymerizable unsaturated bond, For example, film hardening can be performed without impairing optical characteristics.

  Therefore, the display quality of the antireflection film produced by the production method of the present invention, the polarizing plate produced using this antireflection film, and the image display device in which this polarizing plate is disposed can be improved.

  Hereinafter, according to the accompanying drawings, a method for producing a laminate of the present invention, an antireflection film produced by the production method, a polarizing plate using the antireflection film, and the antireflection film or the polarizing plate on the image display surface A preferred embodiment of the arranged image display device will be described in detail.

  FIG. 1 shows a coating / drying apparatus 100 to which the laminate manufacturing method of the present invention is applied, and a gravure coating apparatus 10 is provided as a coating apparatus.

  The gravure coating apparatus 10 mainly includes a gravure roll 1 for coating the web 4 with the coating liquid 2, a coating liquid pan 5 for storing the coating liquid 2 to be supplied to the surface of the gravure roll 1, and the coating liquid 2. It is composed of a doctor blade 3 that scrapes off the excess coating liquid on the surface of the gravure roll 1 by being pressed against the surface of the gravure roll 1 until it comes into contact with the web 4. The gravure roll 1 has an uneven engraving process on the roll surface, and is driven to rotate in the arrow direction Y2 in FIG. 1 by a driving means (not shown). Further, guide rollers 6 a and 6 b are arranged on the upstream side and the downstream side of the gravure roll 1, and the lower end of the guide rollers 6 a and 6 b is lower than the upper end of the gravure roll 1, The gravure roll 1 is pressed relatively.

  The gravure coating apparatus 10 in FIG. 1 is an example of reverse gravure coating (kiss) that rotates the gravure roll 1 in the direction opposite to the conveyance direction of the web 4, but the present invention is not limited to this configuration, and FIG. The present invention can be similarly applied to the configuration by direct gravure coating (direct) shown. The direct gravure coating is configured such that the gravure roll 1 is arranged in parallel with the backup roll 14 being nipped via the web 4 and the gravure roll 1 and the backup roll 14 are rotated in the forward direction with respect to the conveying direction of the web 4. is there. The nip pressure between the backup roll 14 and the gravure roll 1 is adjusted by a cylinder 16 that presses the backup roll shaft.

  Moreover, in FIG.1 and FIG.2, the shape of the uneven | corrugated engraving plate (mesh) formed in the roll surface of the gravure roll 1 is a slanting line (hatched cup), a lattice (trapezoid cup), and a pyramid (pyramid cup). However, the shape of the plate is not limited. Further, the size of the mesh can be freely selected, for example, in the range of # 50 to # 1500. If the mesh is too coarse, the coating amount increases, and the coating amount distribution in the width direction becomes relatively small, but this does not exclude that the mesh is too fine. The gravure roll 1 is basically made of metal, but may be a ceramic gravure roll in which the surface of the metal roll is covered with a ceramic coating for preventing wear and a plate (mesh) is formed on the surface.

  Further, the web 4 may be in the form of a sheet, or may be a strip-like continuous film or a paper base. The width of the web 4 to be used is, for example, about 3 m at the maximum and a thickness of 5 to 300 μm is suitable, but it is not particularly limited. Further, the web 4 is appropriately selected depending on its use, and specifically, a transparent web is used. A plastic film is preferably used as the transparent web. Examples of the polymer forming the plastic film include cellulose ester (eg, triacetyl cellulose, diacetyl cellulose), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, and polyolefin.

According to the gravure coating apparatus 10 configured as described above, the coating liquid of the coating liquid pan 5 is supplied to the surface of the gravure roll 1 by the rotation of the gravure roll 1 and is gravure by the doctor blade 3 pressed against the surface of the gravure roll 1. After the excess coating liquid on the surface of the roll 1 is scraped off, a desired amount of the coating liquid remaining in the recesses on the surface of the gravure roll 1 is applied onto the web 4 that is continuously conveyed in the Y1 direction. Subsequently, the web 4 coated with the coating liquid is conveyed to the drying device 8 via the guide roller 3c, and the coating film is dried while passing through the drying device 8. This coating / drying is repeated at least once, and one or more coating liquids are sequentially applied to the web 4 and dried to produce a laminate. At least one layer of the laminate is a hardened layer formed by applying a coating liquid 2 containing a compound having a polymerizable unsaturated bond with a gravure coating device 10, drying with a drying device 8, and curing. When the layer forms the uppermost layer surface of the laminate, it is possible to impart high hardness characteristics to the laminate and increase the added value of the laminate. In this case, it is preferable that the universal hardness of the layer coated with the coating liquid 2 containing a compound having a polymerizable unsaturated bond is 100 (N / mm ² ) or more. As a result, the quality of the laminate can be improved in the case of various optical functional films such as an optical compensation film used as a retardation plate in a liquid crystal cell, an antireflection film, and an antiglare film. It is.

  However, when the coating liquid 2 containing a compound having many polymerizable unsaturated bonds is applied to the web 4 by using the gravure coating apparatus 10, a failure may occur.

  Therefore, in the method for producing a laminate of the present invention, when forming a laminate by forming one or more films on the web 4 that is continuously transported, at least one of them contains a compound having a polymerizable unsaturated bond. In the manufacturing method of the laminated body which is a hard film layer formed by applying the coating liquid contained by the gravure coating apparatus 10 and then drying by the drying apparatus 8, it is applied when the amount of the polymerizable unsaturated bond is expressed in terms of acrylic equivalent. Under the coating conditions in which the acrylic equivalent of the solid content in the liquid is 3200 (g / mol) or less and the film thickness of the applied layer is 200 nm or less, the uneven processing of the gravure coating apparatus 10 is performed. The material of the doctor blade 3 that is pressed against the surface of the gravure roll 1 applied and scrapes off the excess coating solution before application is at least the contact portion with the gravure roll 1 is resin, or resin and fiber reinforcing material / filling By making the material a composite material, it was made to prevent the occurrence of cracks. Hereinafter, the doctor blade 3 and the compound having many polymerizable unsaturated bonds in the present invention will be described in detail.

(Doctor blade)
As shown in FIG. 3, the doctor blade 3 is held by a blade holder 20 that holds the doctor blade 3. The blade holder 20 includes two pressing plates 21 and 22 that sandwich the proximal end portion of the doctor blade 3, and two metal blocks 23 that exert a clamping force on the doctor blade 3 through the two pressing plates 21 and 22. 24 and fastening bolts 25 and nuts 26 for fastening the metal blocks 23 and 24 to each other. Instead of the fastening bolt 25 and the nut 26, it is possible to obtain a clamping force (a clamping force with respect to the presser plate) by fluid pressure, and the type for obtaining the clamping force of the doctor blade 3 is not particularly limited. The length Lb of the doctor blade 3 protruding from the presser plates 21 and 22 of the blade holder 20 is preferably 1 mm to 50 mm, and more preferably 3 mm to 20 mm. The width Wb of the doctor blade 3 is preferably set wider as the blade length in the longitudinal direction is larger, and is preferably set to 30 mm to 200 mm in order to ensure handling.

  The material of the contact part of the doctor blade 3 with at least the gravure roll 1 is a resin or a composite material in which a resin and a fiber reinforcing material / filler are combined. In this case, not only the contact portion with the gravure roll 1 but also the entire doctor blade 3 may be a resin or a composite material in which a resin and a fiber reinforcing material / filler are combined. A preferable resin is a so-called engineering plastic. Engineering plastics refer to resins that are superior in strength and heat resistance compared to general-purpose thermoplastic resins, and that have high functionality mainly used as mechanical parts for automobiles and electrical parts. Examples of engineering plastics include polycarbonate, modified polyphenylene ether, ultra high molecular weight polyethylene, polyarylate, polysulfone, polyether sulfone, polyetherimide, polyamideimide, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, poly There are ether ether ketone, polyimide, polytetrafluoroethylene and the like.

  A composite material obtained by combining the various engineering plastics and various materials is also preferably used. Composite materials include glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, aramid fiber, boron fiber, asbestos fiber, ceramic fiber and other fiber reinforcements, calcium carbonate, alumina silicate particles, silica sand, inorganic compounds There are fillers such as whiskers.

The material of the doctor blade 3 is preferably a resin having high frictional wear resistance because it is always in contact with the metal gravure roll 1 and is worn by the Taber abrasion test (wear wheel: CS-17, test load: 1000 g, rotation speed: 1000 rotations). The resin should satisfy a test result of 30 (mg / 10 ³ cycle) or less, preferably 20 (mg / 10 ³ cycle) or less. The Taber abrasion test method is stipulated in ASTM D 1044, and two freely rotating wear wheels are kept in contact with a rotating disk-shaped specimen. A constant load is applied to the wear wheel, and the rotation of the test piece causes the test piece surface to contact the wear wheel surface while receiving a constant load, thereby causing ring-shaped wear. The amount of wear is determined by measuring the weight of the sample before and after the test. The test conditions of the Taber friction test in the present invention are a wear wheel: CS-17, a test load: 1000 g, and a rotation speed: 1000 rotations.

  In addition, since the dimensional stability of the doctor blade 3 at the time of application is very important for uniformizing the application surface, the water absorption rate of the material of the doctor blade 3 is 1.0 (%) or less, more preferably 0. .3 (%) or less is preferable. The method for measuring water absorption is specified in ASTM D 570.

  Among the above-mentioned resins, polybutylene terephthalate resin has very strong mechanical strength, low linear expansion coefficient, low water absorption, high dimensional stability, excellent chemical resistance, From the viewpoint of good injection moldability and high accuracy of the doctor blade 3, the material of the doctor blade 3 is particularly preferable. Polyacetal resin is particularly preferable as the material of the doctor blade 3 from the viewpoints of high frictional wear resistance and high machinability. Ultra high molecular weight polyethylene is particularly preferable as the material of the doctor blade 3 from the viewpoints of high frictional wear resistance and high machinability.

  As shown in the enlarged view of the blade tip 3a in FIG. 4, the doctor blade 3 sets the angle (α) of the tip to an acute angle range of 5 ° to 80 °, and the inclined surface 3b of the blade tip 3a The angle with the tangent of the surface of the gravure roll 1 to be pressed is set to be ± 5 ° or less. Thereby, the inclined surface 3b of the blade tip portion and the surface of the gravure roll 1 are pressed flat against each other, and the coating liquid 2 can be stably coated immediately after the start of coating. In addition, a doctor blade 3 having a thickness t1 of 0.05 mm to 1.0 mm is used. Moreover, the thickness t2 (refer FIG. 2) of the presser plates 21 and 22 is 0.3 mm-3 mm.

(Compound with polymerizable unsaturated bond)
The compound having a polymerizable unsaturated bond may be a monomer or a polymer. For example, in the case of a monomer, a monomer having two or more ethylenically unsaturated groups, an ester of a polyhydric alcohol and (meth) acrylic acid (example: Ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane Acrylate, polyester polyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone). ), Acrylamide (eg, methylenebisacrylamide) and methacrylamide.

  Further, a crosslinkable group may be introduced instead of or in addition to the monomer having two or more ethylenically unsaturated groups. Examples of the crosslinkable functional group include an isocyanate group, an epoxy group, an aziridine group, an oxazoline group, an aldehyde group, a carbonyl group, a hydrazine group, a carboxyl group, a methylol group, and an active methylene group. There may be vinyl sulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, metal alkoxide such as tetramethoxysilane, and block isocyanate group. When using these compounds having a crosslinking group, it is necessary to crosslink by application of heat or the like. Other examples include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.

  Examples of other compounds having a polymerizable unsaturated bond include a crosslinkable fluoropolymer compound, and a perfluoroalkyl group-containing silane compound (for example, (heptadecafluoro-1,1,2,2-tetradecyl) tri In addition to ethoxysilane, etc., fluorine-containing copolymers having a fluorine-containing monomer component and a monomer component for imparting a crosslinkable group as constituent components may be mentioned.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole. Etc.), partially (meth) acrylic acid or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) or M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferred, and hexafluoropropylene is particularly preferred from the viewpoints of refractive index, solubility, transparency, availability, and the like.

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups , Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. There are no particular limitations on the monomer units that can be used in combination. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyltoluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tert-butylacrylamide, N- Black hexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

  A preferred form of the copolymer used in the present invention is a copolymer represented by the following general formula 1.

  In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, May have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.

Preferred examples include *-(CH ₂ ) ₂ -O-**, *-(CH ₂ ) ₂ -NH-**, *-(CH ₂ ) ₄ -O-**, *-(CH ₂ ) ₆ -O-**, *-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-**, * -CONH- (CH ₂ ) ₃ -O-**, *-CH ₂ CH (OH ) CH ₂ -O-**, * -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O-** (* represents the linking site on the polymer main chain side, ** represents the linking on the (meth) acryloyl group side Represents a part). m represents 0 or 1;

  In general formula 1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula 1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  A particularly preferred form of the copolymer used in the present invention is represented by the following general formula 2.

  In this general formula 2, X, x, and y have the same meaning as in general formula 1, and the preferred ranges are also the same. n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4. B represents a unit of a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.

  Z1 and Z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.

  For the copolymer represented by the general formula 1 or 2, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized.

  Although the preferable example of the copolymer useful by this invention is shown below, this invention is not limited to these.

When adjusting the coating solution using the compound having a polymerizable unsaturated bond, as described above from the viewpoint of film hardness, the film hardness of the layer obtained by applying the coating solution is the universal hardness. It is preferably 100 (N / mm ² ) or more, and more preferably 125 (N / mm ² ) or more. As a method of adjusting the coating solution for obtaining such universal hardness, the acrylic equivalent of the solid content in the coating solution is 3200 (g / mol) or less when the amount of polymerizable unsaturated bonds is expressed in terms of acrylic equivalent. To be. When the amount of the polymerizable unsaturated bond is taken as another index, the compound having the polymerizable unsaturated bond is 10% by weight or more, more preferably 20% by weight or more of the whole solid in the coating solution. To do.

The universal hardness of the crosslinkable polymer defined in the present invention is the following measurement procedure using a microhardness meter H100 manufactured by Fischer Instruments Co., Ltd. It is represented by the determined universal hardness (N / mm ² ). In other words, select a suitable bar coater so that the cured film thickness after applying and drying the coating solution is about 20-30 μm, and manufactured by TOSHINRIKO.CO.LTD (26 mm x 76 mm x 1.2 mm) polished slide glass plate Apply on top. In the case where the crosslinkable polymer is thermosetting, a thermosetting condition for sufficiently curing the film is obtained in advance (for example, 125 ° C. for 10 minutes), and when the crosslinkable polymer is ionizing radiation curable, the film is similarly formed. The curing conditions for sufficient curing are obtained in advance (as an example, the oxygen concentration is 12 ppm, the UV irradiation amount is 750 mJ / cm ² ). Indentation area for each load F when the conical diamond indenter is pushed in by increasing the load continuously from 0 to 4 mN for each film and making the film thickness of 1/10 that is not affected by the glass plate hardness of the base material maximum Universal hardness is calculated from N = 6 average value of F / A determined from A (mm ² ).

  Next, the polymerization initiator used in combination with the compound having a polymerizable unsaturated bond will be described in detail.

  Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.

  The polymerization initiator (L) of the present invention is a compound that generates radicals when irradiated with light and / or heat. The photopolymerization initiator (L) used in the present invention preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. A compound having a maximum absorption wavelength in the near infrared region can also be used.

  First, the compound (L1) that generates radicals will be described in detail.

  The compound (L1) capable of generating a radical preferably used in the present invention refers to a compound that initiates and accelerates the polymerization of a compound having a polymerizable unsaturated group by generating a radical by irradiation with light and / or heat.

  A known polymerization initiator or a compound having a bond with a small bond dissociation energy can be appropriately selected and used. Moreover, the compound which generate | occur | produces a radical can be used individually or in combination of 2 or more types.

  Examples of the compound that generates radicals include conventionally known organic peroxide compounds, thermal radical polymerization initiators such as azo polymerization initiators, amine compounds (described in Japanese Patent Publication No. 44-20189), organic halogenated compounds, carbonyls, and the like. Examples include photo radical polymerization initiators such as compounds, metallocene compounds, hexaarylbiimidazole compounds, organic boric acid compounds, and disulfone compounds.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A 63-298339, M.M. P. Hut "Journal of Heterocyclic Chemistry" 1 (No3), (1970) "and the like, and in particular, an oxazole compound substituted with a trihalomethyl group: S-triazine compound.

  More preferred are s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring.

  Examples of other organic halogen compounds include ketones, sulfides, sulfones and nitrogen-containing heterocycles described in paragraphs [0039] to [0048] of JP-A-5-27830.

  Examples of the carbonyl compound include, for example, “Latest UV Curing Technology”, pages 60 to 62 (published by Technical Information Association, 1991), paragraph numbers [0015] to [0016] of JP-A-8-134404, And the compounds described in paragraph Nos. [0029] to [0031] of the specification of No. 11-217518, and benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, benzoin isobutyl ether Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, benzyldimethyl ketal, and acylphosphine oxide.

  Examples of the organic peroxide compound include compounds described in paragraph [0019] of JP-A No. 2001-139663.

  Examples of the metallocene compound include various titanocene compounds described in JP-A-2-4705 and JP-A-5-83588, iron-arene complexes described in JP-A-1-304453, JP-A-1-152109, and the like. Is mentioned.

  Examples of the hexaarylbiimidazole compound described in JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, 4,622,286, and the like. And various compounds.

  Examples of the organic borate compound include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Examples of the organic borate described are the compounds described. For example, the compounds described in paragraphs [0022] to [0027] of JP-A-2002-116539 can be mentioned.

  As other organic boron compounds, organic boron such as JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, JP-A-7-292014, etc. Specific examples include transition metal coordination complexes and the like.

  Examples of the sulfone compound include compounds described in JP-A-5-239015, and examples of the disulfone compound include those represented by general formulas (II) and (III) described in JP-A 61-166544. Compounds and the like.

  These radical generating compounds may be used alone or in combination of two or more. As addition amount, it is 0.1-30 mass% with respect to the whole quantity of a radically polymerizable monomer, Preferably it is 0.5-25 mass%, Most preferably, it can add at 1-20 mass%. Within this range, the polymerizability is high.

  It is preferable that the composition of this invention contains a radical polymerization initiator in the ratio of 0.5-10 mass% with respect to the total mass of the compound containing a polymerizable unsaturated bond. More preferably, it contains a radical polymerization initiator in a proportion of 1 to 5% by mass.

  In the composition of the present invention, when a polymerization reaction is carried out by ultraviolet irradiation, a conventionally known ultraviolet spectral sensitizer or chemical sensitizer may be used in combination. Examples include Michler's ketone, amino acids (such as glycine), and organic amines (such as butylamine and dibutylamine).

  Moreover, when performing a polymerization reaction by near infrared irradiation, it is preferable to use a near infrared spectral sensitizer together.

  The near-infrared spectral sensitizer used in combination may be a light-absorbing substance having an absorption band in at least a part of the wavelength range of 700 nm or more, and a compound having a molecular extinction coefficient of 10,000 or more is preferable. Furthermore, a value having absorption in the region of 750 to 1400 nm and a molecular extinction coefficient of 20000 or more is preferable. Moreover, it is more preferable that there is a trough of absorption in the visible light wavelength region of 420 nm to 700 nm, and it is optically transparent. As the near-infrared spectral sensitizer, various pigments and dyes known as near-infrared absorbing pigments and near-infrared absorbing dyes can be used. Among these, it is preferable to use a conventionally known near-infrared absorber.

  Commercially available dyes and literature (for example, “Chemical Industry”, May 1986, p. 45-51, “Near Infrared Absorbing Dye”, “Development and Market Trends of Functional Dyes in the 90s”, Chapter 2.3. (1990) CMC), “special function pigments” (edited by Ikemori and Piladani, 1986, issued by CMC Corporation), J. Am. FABIAN, Chem. Rev., 92, pp 1197 to 1226 (1992), a catalog published in 1995 by Nippon Sensitive Dye Research Institute, Exciton Inc. Known dyes described in the laser dye catalog or patent issued in 1989.

  FIG. 5 is an example of the case where the laminate produced by the production method of the present invention is an antireflection film.

  As shown in FIG. 5, the antireflection film comprises a transparent support (1), a hard coat layer (2), a medium refractive index layer (3), a high refractive index layer (4), and a low refractive index layer (5). The layer structure is as follows. Such an antireflection film having three refractive layers has an optical film thickness of each of the medium refractive index layer, the high refractive index layer, and the low refractive index layer, that is, the product of the refractive index and the film thickness is the design wavelength λ. However, it is described in JP-A-59-50401 that it is preferably about nλ / 4 or a multiple thereof. However, in order to realize a reflectance characteristic with a low reflectance and a reduced color of reflected light, the middle refractive index layer has the following formula (I) particularly for the design wavelength λ (= 400 nm to 680 nm). The high refractive index layer must satisfy the following formula (II), and the low refractive index layer must satisfy the following formula (III). The design wavelength is desirably 400 nm to 600 nm, more desirably 450 nm to 550 nm, and most desirably 475 nm to 525 nm.

lλ / 4 × 0.80 <n1d1 <lλ / 4 × 1.00 (I)
mλ / 4 × 0.75 <n2d2 <mλ / 4 × 0.95 (II)
nλ / 4 × 0.95 <n3d3 <nλ / 4 × 1.05 (III)
Where l (lowercase L) is 1, n1 is the refractive index of the medium refractive index layer, and d1 is the layer thickness (nm) of the medium refractive index layer, m is 2, n2 Is the refractive index of the high refractive index layer, and d2 is the layer thickness (nm) of the high refractive index layer, n is 1, n3 is the refractive index of the low refractive index layer, and d3 is The layer thickness (nm) of the low refractive index layer. Furthermore, for example, n1 is 1.60 to 1.65 and n2 is 1 for a transparent support having a refractive index of 1.45 to 1.55 made of triacetylcellulose (refractive index: 1.49). .85 to 1.95, n3 must have a refractive index of 1.35 to 1.45, for example, a refractive index of 1.55 to 1.65 made of polyethylene terephthalate (refractive index: 1.66). N1 is 1.65 to 1.75, n2 is 1.85 to 2.05, and n3 is 1.35 to 1.45. When materials of medium refractive index layer and high refractive index layer having the above refractive index cannot be selected, an equivalent combination of a layer having a refractive index higher than the set refractive index and a layer having a low refractive index is combined. It is known that a film layer can be used to form a layer that is optically equivalent to a medium refractive index layer or a high refractive index layer having a set refractive index, and also to realize the reflectance characteristics of the present invention. Can be used. The “substantially three layers” of the present invention includes an antireflection layer composed of terms having different refractive indexes of four layers and five layers using such an equivalent film.

  6 to 11 show various forms of the layer structure of the antireflection film. . As shown in FIGS. 6 to 11, when the low refractive index layer (5) is laminated as a refractive index layer on the support (1) or the hard coat layer (2) applied on the support (1). It can be suitably used as an antireflection film. Furthermore, even if a high refractive index layer (4) and a low refractive index layer (5) are laminated on the support (1) or the hard coat layer (2) applied on the support (1), antireflection is provided. It can be suitably used as a film. The hard coat layer may have antiglare properties. The antiglare property may be due to dispersion of mat particles, or may be formed by surface shaping by a method such as embossing.

  When the antireflection film produced by the production method of the present invention is used as one side of the surface protective film of the polarizer, the surface of the transparent support opposite to the surface on which the antireflection layer is formed is saponified with alkali. It is necessary to process. Specific means for the alkali saponification treatment can be selected from the following two. (1) is superior in that it can be processed in the same process as a general-purpose triacetyl cellulose film, but since the surface of the antireflection film is saponified, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.

  (1) After the antireflection layer is formed on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once. (2) Before or after the formation of the antireflection layer on the transparent support, the alkaline liquid is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, and is heated, washed and / or washed. By summing, only the back surface of the film is saponified.

  Examples of the polarizer include an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer. In general, a polyvinyl alcohol film (hereinafter referred to as PVA) is preferably used as the iodine polarizer and the dye polarizer. PVA is usually saponified polyvinyl acetate, but modified PVA can also be used. A polarizing film is obtained by dyeing PVA. Examples of dyeing can be performed by any means such as a method of immersing a PVA film in an iodine-potassium iodide aqueous solution, application or spraying of iodine or a dye solution. In the process of producing a polarizing film by stretching PVA, it is preferable to use an additive that crosslinks PVA, for example, boric acids. The transmittance of the polarizing plate is preferably in the range of 30 to 50% and more preferably in the range of 35 to 50% with respect to light having a wavelength of 550 nm. The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.

  When the antireflection film produced by the production method of the present invention is used as one side of a surface protective film of a polarizer, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane It can be preferably used for transmissive, reflective, or transflective liquid crystal display devices in modes such as switching (IPS) and optically compensatory bend cells (OCB). When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained. In addition, when a front plate such as an acrylic plate is arranged over the entire surface of the liquid crystal cell in a transmissive, reflective, and transflective liquid crystal display device, not only the polarizing plate on the liquid crystal cell surface side, Adhering to the inner side and / or the outer side of the front plate via an adhesive or the like and reducing reflection at the interface are preferable. Further, by combining with a λ / 4 plate, it can be used as a reflective or transflective LCD or a surface protection plate for an organic EL display. In addition, the antireflection layer of the present invention is formed on a transparent support such as PET or PEN, and the surface protection plate of a PDA, a cellular phone, a touch panel, a plasma display panel (PDP), or a cathode ray tube display (CRT). It can be applied to various image display devices.

  Although the Example of the manufacturing method of the laminated body of this invention is described in detail below, this invention is not limited to these.

  In this example, the relationship between the amount of polymerizable unsaturated bonds in the solid content of the coating solution and the failure, the relationship between the film thickness in the applied dry film state and the failure, and the material of the doctor blade 3 The relationship with the fault was investigated.

  First, five types of coating solutions for low refractive index layers (LL-1 to LL-5) having different amounts of polymerizable unsaturated bonds in the solid content in the coating solution were prepared.

(Preparation of coating solution LL-1 for low refractive index layer)
In 193 g of cyclohexanone and 623 g of methyl ethyl ketone, 1.7 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and 1.7 g of reactive silicone (X-22-164C, manufactured by Shin-Etsu Chemical Co., Ltd.) were dissolved. Further, 182 g of a 18.4 mass percent methyl ethyl ketone solution of the following fluorine-containing copolymer was added, and after stirring, the mixture was filtered with a polypropylene filter (PPE-03) having a pore size of 3 μm to obtain a coating solution for a low refractive index layer ( LL-1) was prepared. The acrylic equivalent of the coating solution for low refractive index layer (LL-1) is 320 (g / mol). The fluorine-based copolymer is as shown below.

(Preparation of coating solution for low refractive index layer (LL-2))
Thermally crosslinkable fluorinated polymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation) 177 g and silica sol (MEK-ST, average particle size 10-20 nm, solid content concentration 30%, (Nissan Chemical Co., Ltd.) 15.2 g, γ-acryloxypropyltrimethoxysilane (KBM-5103, Shin-Etsu Chemical Co., Ltd.) 4.5 g, methyl ethyl ketone 95 g, cyclohexanone 9.0 g were added, and after stirring, the pore size was 1 μm. The solution was filtered through a polypropylene filter to prepare a coating solution for low refractive index layer (LL-2). This low refractive index layer coating solution (LL-2) does not contain a polymerizable unsaturated bond. Therefore, since the acrylic equivalent is infinite (∞), it is indicated by ∞ in the acrylic equivalent column of FIG.

(Preparation of coating solution for low refractive index layer (LL-3))
177 g of a heat-crosslinkable fluoropolymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation), 0.12 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and silica sol ( MEK-ST, average particle size 10 to 20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 15.2 g, γ-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) 4.5 g, 12.1 g of a 18.4 mass percent methyl ethyl ketone solution of the above fluorinated copolymer, 95 g of methyl ethyl ketone, and 9.0 g of cyclohexanone were added. After stirring, the solution was filtered with a polypropylene filter having a pore size of 1 μm for a low refractive index layer. A coating solution (LL-3) was prepared. The acrylic equivalent of the coating solution for low refractive index layer (LL-3) is 6100 (g / mol).

(Preparation of coating solution for low refractive index layer (LL-4))
177 g of a heat-crosslinkable fluoropolymer having a refractive index of 1.42 (JN-7228, solid content concentration 6%, manufactured by JSR Corporation), 0.23 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and silica sol ( MEK-ST, average particle size 10 to 20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 15.2 g, γ-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) 4.5 g, Add 24.2 g of 18.4 mass percent methyl ethyl ketone solution of the above fluorinated copolymer, 95 g of methyl ethyl ketone, and 9.0 g of cyclohexanone, and after stirring, filter through a polypropylene filter having a pore size of 1 μm for the low refractive index layer. A coating solution (LL-4) was prepared. The acrylic equivalent of the coating solution for low refractive index layer (LL-4) is 3200 (g / mol).

(Preparation of coating solution for low refractive index layer (LL-5))
177 g of a heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN-7228, solid concentration 6%, manufactured by JSR Corporation), 0.35 g of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) and silica sol (MEK) -ST, average particle size 10 to 20 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 15.2 g, γ-acryloxypropyltrimethoxysilane (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) 4.5 g, the above 36.3 g of a 18.4 mass percent methyl ethyl ketone solution and 95 g of methyl ethyl ketone and 9.0 g of cyclohexanone were added. After stirring, the solution was filtered through a polypropylene filter having a pore size of 1 μm to apply for a low refractive index layer. A liquid (LL-5) was prepared. The acrylic equivalent of the coating solution for low refractive index layer (LL-5) is 2200 (g / mol).

[Example 1]
In Example 1, the relationship between the material of the doctor blade 3 and the failure was investigated. That is, the low refractive index layer coating solution LL-1 was used, and the low refractive index layer prepared using the polyacetal doctor blade 3 and the metal (steel: SK material) doctor blade 3 were used. We compared the occurrence of bumps on the film surface with the low refractive index layer.

(Test 1)
The surface on the application side of a polyethylene terephthalate film having a film thickness of 100 μm was subjected to a static elimination process with an ultrasonic dust remover, and a low refractive index layer coating solution (LL-1) was applied using a gravure coating apparatus 10. As the doctor blade 3, a doctor blade 3 made of polyacetal was used. An enlarged view of a portion of the doctor blade 3 that contacts the gravure roll 1 is shown in FIG. The conditions of the doctor blade 3 were such that the thickness t1 of the bulk portion was 760 μm, the length L of the unprocessed portion of the tip portion 3a of the doctor blade 3 was 690 μm, and the cutting angle β was 20 °.

The drying condition in the low refractive index layer drying apparatus 8 is 90 ° C. for 30 seconds, and the ultraviolet curing condition is an air-cooled metal halide lamp (240 W / cm) while purging with nitrogen so that the oxygen concentration is 0.1 vol% or less. The amount of irradiation was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .

  The low refractive index layer after curing had a refractive index of 1.440 and a film thickness of 85 nm. In this way, a low refractive index layer was produced.

  In the above, the coating / drying step is performed in an air atmosphere having an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 is just before coating. High air was blown at a high speed to separate the deposits from the film surface, and coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the web 4 before dust removal was 200 V or less. The production of the low refractive index layer was carried out in the following steps: delivery, dust removal, application, drying, (UV or heat) curing, and winding.

(Test 2)
A low refractive index layer was produced under the same conditions as in Test 1 except that the material of the doctor blade 3 was changed to metal (SK material). In FIG. 12, the shape of the doctor blade 3 is such that the bulk portion thickness t1 is 150 μm, the length L of the unprocessed portion of the tip portion 3a of the doctor blade 3 is 75 μm, and the scraping angle β is 20 °. In the following test, the thickness t1 of the bulk portion of the unprocessed portion of the metal (SK material) doctor blade 3, the length L of the unprocessed portion of the tip portion 3a, and the cutting angle β are the same.

[Example 2]
In Example 2, the relationship between the amount of polymerizable unsaturated bonds in the solid content in the coating solution and the failure was investigated. That is, when the low refractive index layer was produced by changing the coating solution for the low refractive index layer from LL2 (Test 3) to LL5 (Test 6) using a metal doctor blade 3, the occurrence of irregularities on the film surface I investigated.

(Test 3)
The type of the coating solution for the low refractive index layer was changed from LL-1 to LL-2, and the coating solution for the low refractive index layer was applied using the gravure coating apparatus 10. The doctor blade 3 was made of metal (SK material). After coating, drying is performed at 100 ° C. for 2 minutes in a drying apparatus 8, and then a 160 W / cm air-cooled metal halide lamp (I Graphics Co., Ltd.) is purged with nitrogen so that the oxygen concentration becomes 2% by volume or less. The low refractive index layer was produced by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² and heating at 120 ° C. for 10 minutes. The low refractive index layer after curing had a refractive index of 1.430 and a film thickness of 86 nm.

(Test 4)
A low refractive index layer was produced under the same conditions as in Test 3 except that the type of coating solution for the low refractive index layer was changed from LL-2 to LL-3.

(Test 5)
A low refractive index layer was produced under the same conditions as in Test 3 except that the type of coating solution for the low refractive index layer was changed from LL-2 to LL-4.

(Test 6)
A low refractive index layer was produced under the same conditions as in Example 3 except that the type of coating solution for the low refractive index layer was changed from LL-2 to LL-5.

[Example 3]
In Example 3, the relationship between the film thickness in the applied dry film state and the failure was investigated. That is, using the coating liquid LL-1 for the low refractive index layer and using a metal doctor blade 3, the film thickness in the dry film state is 150 nm (Test 7), 200 nm (Test 8), 250 nm (Test 9). The low refractive index layers were prepared so that the occurrence of irregularities on the film surface of each low refractive index layer was investigated.

(Test 7)
A low refractive index layer was produced under the same conditions as in Test 2 except that the film thickness of the low refractive index layer was changed to 150 nm.

(Test 8)
A low refractive index layer was produced under the same conditions as in Test 2 except that the film thickness of the low refractive index layer was changed to 200 nm.

(Test 9)
A low refractive index layer was produced under the same conditions as in Test 2 except that the film thickness of the low refractive index layer was changed to 250 nm.

[Example 4]
In Example 4, it was examined what happens to the occurrence of irregularities on the film surface of the low refractive index layer when the type of resin forming the doctor blade 3 is changed.

(Test 10)
A low refractive index layer was produced under the same conditions as in Test 1 except that the material of the doctor blade 3 was changed to high density polyethylene.

(Test 11)
A low refractive index layer was produced under the same conditions as in Test 1 except that the material of the doctor blade 3 was changed to nylon 66.

(Test 12)
A low refractive index layer was produced under the same conditions as in Test 1 except that the material of the doctor blade 3 was changed to polybutylene terephthalate.

(Test 13)
A low refractive index layer was produced under the same conditions as in Test 1 except that the material of the doctor blade 3 was changed to ultrahigh molecular weight polyethylene.

  The test conditions and test results of Test 1 to Test 13 described above are shown in FIG.

As an evaluation method of the number of bumps in the produced low refractive index layer, the film surface of the low refractive index layer was observed with an optical microscope, and a comparison was made according to the number of bumps per 0.1 mm ² , that is, the density of the bumps. Items with a diameter of 1 μm or more were counted. If the number of protrusions is 10 or less per 0.1 mm ^2, the film surface of the low refractive index layer is not visually whitish, and the quality is acceptable. In addition, the number of streaks per 1 m width was counted. Furthermore, visual judgment was performed about the change of the surface shape at the time of performing continuous application for 600 minutes. As for the streak, if it is even about 1 m in width, the color becomes uneven, which is not preferable.

  Regarding the density of bumps, first, test 1 and test 2 are compared. If the material of the doctor blade 3 is steel (made of metal), a crack failure occurs, but the material of the doctor blade 3 is made of resin. By doing this, it can be seen that the occurrence of a fault is suppressed. In addition, when the test blades 3 made of various resins of tests 10 to 13 were used, the number of the test pieces was 10 or less, and the test density was higher than that of the test 2 using the steel doctor blade 3. It can be seen that is decreasing.

  Further, from the tests 3 to 6, the relationship between the amount of polymerizable unsaturated bonds and the failure is considered. As shown in test 3, the acrylic equivalent of the solid content in the coating solution is ∞ (no polymerizable unsaturated bonds). ) Or when the acrylic equivalent is 6100 (g / mol) and the amount of polymerizable unsaturated bonds is small, as in Test 4, the number of bumps is 0 or 3, and the metal doctor blade 3 Even so, the fault is at a level where there is virtually no problem.

  However, as in Tests 3 to 6, as the acrylic equivalent is reduced, that is, as the amount of polymerizable unsaturated bonds is increased, the number of bumps gradually increases, and the acrylic equivalent is 3200 (g / mol). The number of irregularities becomes 10, which matches the standard number. When the acrylic equivalent is 2200 (g / mol), the number of bumps is 15, which greatly exceeds the standard number of 10. For reference, when the acrylic equivalent is 320 (g / mol) and the amount of polymerizable unsaturated bonds is large as in Test 2, the number of bumps is 40.

  On the other hand, when the resin doctor blade 3 is used as in Test 1 and Tests 10 to 13, the number of bumps is 5 or less even if the acrylic equivalent is 320 (g / mol). Good result.

  From this result, under the condition of the coating solution having a large amount of polymerizable unsaturated bonds such as an acrylic equivalent of 3200 (g / mol) or less, the resin layer 3 is not used unless the resin doctor blade 3 is used. It can be seen that the film surface becomes whitish due to a fault.

  Next, from Test 7 to Test 9, considering the relationship between the film thickness (dry film) of the low refractive index layer and the failure, if the film thickness of the low refractive index layer is 250 nm as in Test 9, the metal Even in the case of the doctor blade 3 made of metal, no fault is observed.

  However, as can be seen from Test 7 to Test 9, the number of bumps increases as the film thickness decreases, and in the case of a metal doctor blade 3, the number of bumps is 10 in Test 8 with a film thickness of 200 nm. In the test 7 where the film thickness is 150 nm, the number of bumps is 18 and greatly exceeds the standard.

  On the other hand, when the resin doctor blade 3 is used as in Test 1 and Tests 10 to 13, no faults occur even if the film thickness is 85 nm. In this case, the acrylic equivalent in Test 7 to Test 9, Test 1 and Test 10 to 13 is the same.

  From this result, it can be seen that the film surface of the low refractive index layer becomes whitish due to a blister failure unless the resin doctor blade 3 is used under a coating condition in which a thin film having a thickness of 200 nm or less is applied.

  For streaks, polyacetal doctor blades (Test 1), steel doctor blades (Test 2), high-density polyethylene doctor blades (Test 10), polybutylene terephthalate doctor blades with good moldability (Test 12) Although the doctor blade made of ultra high molecular weight polyethylene (Test 13) is relatively good, the doctor blade 3 made of nylon 66 of Test 11 changes the dimensions of the doctor blade 3 due to water absorption, and the doctor blade 3 The flatness of the tip end portion a could not be maintained and many streaks were generated.

  Further, after 600 minutes of continuous application, in the doctor blade 3 made of high-density polyethylene of Test 2 with low wear resistance, the scraping property changes due to the progress of wear, and the shape of the tip 3a of the doctor blade 3 changes. A decrease in thickness and the number of streaks were observed.

  From this result, it can be seen that among the types of resins, polyacetal resin, polybutylene terephthalate resin, and ultrahigh molecular weight polyethylene resin are particularly preferable as the material of the doctor blade 3.

[Example 4]
In Example 4, a low refractive index layer prepared with the coating solution LL-1 for low refractive index layer having many polymerizable unsaturated bonds having an acrylic equivalent of 320 (g / mol), an acrylic equivalent of ∞, The universal hardness was compared with that of the low refractive index layer prepared with the coating solution LL-3 for the low refractive index layer having no saturated bond.

(Test 14)
Select a suitable bar coater so that the film thickness after curing of the coating solution of LL-1 and LL-2 is about 20 to 30 μm, and it is made by TOSHINRIKO.CO.LTD (26 mm x 76 mm x 1.2 mm) It apply | coated on the glass plate. For the coating film coated with LL-1, the solvent was sufficiently evaporated, followed by UV curing. The UV curing conditions were as follows: irradiation with an illuminance of 600 mW / cm ² using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. Irradiation was performed at an irradiation amount of 600 mJ / cm ² to form a film.

In addition, the coating film coated with LL-2 was dried at 100 ° C. for 2 minutes and then purged with nitrogen so that the atmosphere had an oxygen concentration of 2% by volume or less, and a 160 W / cm air-cooled metal halide lamp ( Using an iGraphics Co., Ltd., ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ² were irradiated and heated at 120 ° C. for 10 minutes to form a film. Universal hardness was measured with respect to each obtained film | membrane using the microhardness meter H100 by Fischer Instruments. From the depression area A (mm ² ) for each load F when the load is continuously increased from 0 to 4 mN and the conical diamond indenter is pushed in with the maximum 1/10 film thickness not affected by the glass plate hardness of the substrate. The universal hardness was calculated from the measured F / A N = 6 average value.

As a result, the universal hardness of the film obtained by applying, drying and curing LL-1 is 170 (N / mm ² ), whereas the universal hardness of the film obtained by applying, drying and curing LL-2. The hardness was 80 (N / mm ² ). This shows that the film hardness cannot be secured with a film coated with LL-2 having no polymerizable unsaturated bond.

[Example 5]
In Example 5, when the resin doctor blade 3 is used and when the metal doctor blade 3 is used, the web, hard coat layer, medium refractive index layer, high refractive index layer, low An antireflection film composed of a refractive index layer was produced and evaluated for quality.

(Preparation of hard coat layer coating solution (HCL-1))
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.

  That is, 750.0 parts by weight of trimethylolpropane triacrylate (TMPTA, manufactured by Nippon Kayaku Co., Ltd.), 270.0 parts by weight of poly (glycidyl methacrylate) having a weight average molecular weight of 15000, 730.0 parts by weight of methyl ethyl ketone, and 500 cyclohexanone. 0.0 part by mass and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Japan, Inc.) were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

(Preparation of titanium dioxide fine particle dispersion)
As titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO2: Co3O4: Al2O3: ZrO2 = containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide = 90.5: 3.0: 4.0: 0.5 weight ratio).

  The following dispersant (D-2) 41.1 parts by mass and cyclohexanone 701.8 parts by mass are added to 257.1 parts by mass of these particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a weight average diameter of 70 nm. did.

(Preparation of medium refractive index layer coating solution (ML-1))
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.6 parts by mass of a photopolymerization initiator (Irgacure 907), light A sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by mass, 279.6 parts by mass of methyl ethyl ketone and 1049.0 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for the middle refractive index layer (ML-1).

(Preparation of coating solution for high refractive index layer (HL-1))
To 469.8 parts by mass of the above-mentioned titanium dioxide dispersion A, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Geigy Co., Ltd.), 1.1 parts by mass of photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and 459.6 parts by mass of cyclohexanone. Parts were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

(Preparation of antireflection film)
With an ultrasonic dust remover, the surface on the application side of a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) with a film thickness of 80 μm is subjected to static elimination treatment, and then the hard coat layer coating liquid (HCL-1) is applied. The gravure coating apparatus 10 was used for coating. After drying at 80 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^{2. The} coating layer was cured by irradiating with an irradiation amount of 500 mJ / cm ² to form a hard coat layer having a thickness of 8 μm. On the hard coat layer, a medium refractive index layer coating solution (ML-1) was coated using a gravure coating apparatus 10. A polyacetal blade was used as the doctor blade 3. The enlarged view of the portion of the doctor blade 3 that comes into contact with the gravure roll 1 is the same as that already described with reference to FIG. After drying at 100 ° C., using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, an illuminance of 550 mW / The coating layer was cured by irradiating with an ultraviolet ray of cm ² and an irradiation amount of 550 mJ / cm ² to form a medium refractive index layer (refractive index 1.63, film thickness 70 nm).

A high refractive index layer coating solution (HL-1) was applied onto the middle refractive index layer using the gravure coating apparatus 10. As the doctor blade 3, a doctor blade 3 made of polyacetal was used. The enlarged view of the part which contacts the gravure roll 1 of the doctor blade 3 is as shown in FIG. 12, and is the same as the case of the middle refractive index layer. After drying at 100 ° C., using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol% or less, an illuminance of 550 mW / cm ^2, an irradiation dose of 550 mJ / cm ^2, to form a high refractive index layer (refractive index 1.90, film thickness 107 nm).

  On the high refractive index layer, the coating solution for low refractive index layer (LL-1) prepared in Example 1 was applied using a gravure coating apparatus 10. As the doctor blade 3, a doctor blade 3 made of polyacetal was used. The enlarged view of the portion of the doctor blade 3 that comes into contact with the gravure roll 1 is as already described with reference to FIG. 12, and is the same as in the case of the medium refractive index layer.

The low refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. The irradiance was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .

  The low refractive index layer after curing had a refractive index of 1.440 and a film thickness of 85 nm. In this way, an antireflection film was produced.

  In the above, the coating and drying steps are performed in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 is just before the coating. High air was blown at a high speed to separate the deposits from the film surface, and coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the web 4 before dust removal was 200 V or less. The above coating was performed for each layer in the following steps: delivery, dust removal, coating, drying, (UV or heat) curing, and winding.

(Test 16)
An antireflection film was produced under the same conditions as in Test 15 except that the material of the doctor blade 3 was changed to steel (SK material). The part of the doctor blade 3 in contact with the gravure roll 1 was also the same as in the test 15.

  Then, using the antireflection film obtained in Test 15 and Test 16, a polarizing plate with antireflection was prepared. Using this polarizing plate, a liquid crystal display device having an antireflection layer disposed on the outermost layer was produced. As a result, the liquid crystal display device using the antireflection film of Test 15 had excellent contrast because it had little reflection of external light. Furthermore, there was no coloration over the entire display device, and a high-quality image could be obtained.

  On the other hand, in the liquid crystal display device using the antireflection film of Test 16, the whiteness of the surface increased due to the occurrence of a fault, and the display quality deteriorated.

The conceptual diagram which showed the outline of the coating and drying apparatus which applies the manufacturing method of the laminated body of this invention The conceptual diagram which showed the outline of the direct gravure coating device among the gravure coating devices Sectional view showing doctor blade holding structure Explanatory drawing explaining the tip of the doctor blade Explanatory drawing explaining an example of the layer structure of an antireflection film Explanatory drawing explaining other examples of layer composition of an antireflection film Explanatory drawing explaining the further another example of the layer structure of an antireflection film Explanatory drawing explaining the further another example of the layer structure of an antireflection film Explanatory drawing explaining the further another example of the layer structure of an antireflection film Explanatory drawing explaining the further another example of the layer structure of an antireflection film Explanatory drawing explaining the further another example of the layer structure of an antireflection film Explanatory drawing explaining the front-end | tip part of the doctor blade used in the Example Table showing the conditions and results of the examples

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Gravure roll, 2 ... Coating liquid, 3 ... Doctor blade, 3a ... Doctor blade tip part, 4 ... Web, 5 ... Coating liquid pan, 6a, 6b, 6c ... Guide roller, 8 ... Drying device, 10 ... Gravure coating Device: 14 ... Backup roll, 16 ... Cylinder, 20 ... Blade holder, 21, 22 ... Press plate, 23, 24 ... Metal block, 25 ... Fastening bolt, 26 ... Nut, 100 ... Application / drying device

Claims (11)

When forming a laminated body by forming one or more films on a continuous support that is continuously conveyed, at least one of the layers is coated with a gravure coating apparatus containing a compound having a polymerizable unsaturated bond. In the method for producing a laminate, which is a dura layer formed by drying after drying with a drying apparatus,
When the amount of the polymerizable unsaturated bond is expressed in terms of acrylic equivalent, the acrylic equivalent of the solid content in the coating solution is 3200 (g / mol) or less, and the thickness of the applied layer in the dry state is Under coating conditions of 200 nm or less, the material of at least the contact portion of the doctor blade that presses against the surface of the gravure roll of the gravure coating apparatus and scrapes off the excess coating liquid prior to coating is resin or resin A method for producing a laminate, which is a composite material obtained by combining a fiber reinforcement and a filler. The material of at least the contact part of the doctor blade satisfies a wear test result of 30 (mg / 10 ³ cycle) or less according to the Taber abrasion test (wear wheel: CS-17, test load: 1000 g, rotation speed: 1000 rotations) The method for producing a laminate according to claim 1, wherein the laminate is made of a material to be manufactured.   3. The method for manufacturing a laminate according to claim 1, wherein the doctor blade has a water absorption of 1.0 (%) or less after the doctor blade is immersed in water for 24 hours. The laminate according to any one of claims 1 to 3, wherein a universal hardness of a layer coated with a coating solution containing a compound having a polymerizable unsaturated bond is 100 (N / mm ² ) or more. Body manufacturing method.   The method for producing a laminate according to any one of claims 1 to 4, wherein a material of at least the contact portion of the doctor blade is a polyacetal resin.   The method for producing a laminate according to any one of claims 1 to 4, wherein a material of at least the contact portion of the doctor blade is a polybutylene terephthalate resin.   The method for producing a laminate according to any one of claims 1 to 4, wherein a material of at least the contact portion of the doctor blade is an ultrahigh molecular weight polyethylene resin.   8. The compound according to claim 1, wherein the compound having a polymerizable unsaturated bond is a copolymer containing at least one kind of a polymerizable unsaturated bond group-containing polymerization component and a fluorine-containing polymerization component. The manufacturing method of the laminated body of Claim 1.   An antireflection film manufactured by the method for manufacturing a laminate according to any one of claims 1 to 8.   A polarizing plate, wherein the polarizing film is produced using the antireflection film according to claim 9.   An image display device, wherein the antireflection film according to claim 9 or the polarizing plate according to claim 10 is disposed on an image display surface.

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